Ionothermal synthesis is a strongly growing research area due to the outstanding physical and chemical properties of ionic liquids (ILs) in the design of new materials, however, the interaction of these IL molecules with optical materials and their effect on the luminescence properties of the materials are poorly known. In this work, it is shown that the imidazolium based BmimBF4 ionic liquid, used as a solvent during the synthesis, tethers at the surface of the nanoparticles and influences the photoluminescence of the nanophosphor BaFBr:Eu2+ materials. In time resolved spectra, two different emissions are observed for the material synthesized by the ionothermal approach, one corresponding to Eu(II) 5d–4f transitions in the BaFBr host with a decay time of 843 ns and the other with a much faster decay time compared to the ionic liquid BmimBF4.